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This paper describes the use of gas chromatography/mass spectroscopy (GC/MS) using static headspace sampling for the determination of furan in irradiated fruit and vegetable juice. The data presented demonstrate that furan is generated in juice as a result of treatment with ionizing radiation, but at low part-per-billion concentrations. The amount of furan increases with increasing dose in a non-linear second order relationship. Furthermore, it was found that furan interacts with the ionizing radiation in such a way that the amount of furan can be reduced in the absence of precursor compounds commonly found in juice products. Several possible precursors have been identified, including glucose, fructose, and ascorbic acid. We conclude that the formation of furan is complex and proceeds through a multi step process.

A headspace gas chromatography/mass spectrometry method was developed and validated in-house for the determination of furan in foods. The method of standard additions with d4-furan as the internal standard was used to quantitate furan. The limit of detection and limit of quantitation (LOQ) values ranged from 0.2 and 0.6 ng/g, respectively, in apple juice to 0.9 and 2.9 ng/g, respectively, in peanut butter. Recoveries were obtained at 0.5, 1, 2, and 3 times the LOQ. At 1, 2, and 3 times the LOQ, the recoveries ranged from 89.4 to 108%, and the relative standard deviations ranged from 3.3 to 17.3% for all the matrixes. For apple juice, chicken broth, and infant formula, the averaged coefficients of determination from the linear regression analyses were >0.99 with each food fortified at 0.5, 1, 2, and 3 times the LOQ. The coefficients of determination were >0.99 for green beans and 0.96 for peanut butter with the foods fortified at 1, 2, and 3 times the LOQ. Within-laboratory precision was determined by comparing the amounts of furan found in 18 samples by 2 analysts on different days with different instruments. For most of the foods, the difference between the amounts found by each analyst was 300 foods. The furan levels found ranged from none detected to 174 ng/g.

Two semi-rigid amorphous polyethylene terephthalate copolymer materials (in both sheet and powder forms) containing 3% 1,4-cyclohexane dimethanol (CHDM) and 31% CHDM were irradiated at 5, 25 and 50 kGy at ambient temperature with a (60)Co radiator or an electron-beam accelerator. After irradiation, volatiles were determined using static headspace sampling with capillary gas chromatography and mass selective detection or flame ionization detection (HS/GC/MSD or FID). Non-volatiles were extracted with 10% aqueous ethanol and 100% n-heptane food-simulating solvents, maintained at 40 degrees C for up to 10 days. The non-volatiles in the materials and those migrating into the food-simulating solvents were determined by high-performance liquid chromatography (HPLC) with ultraviolet and/or photodiode array detection. The results obtained from the HS/GC/MSD suggest that no new chemicals were detected by either gamma- or e-beam irradiation when compared with non-irradiated specimens. The major volatiles in the copolymers were acetaldehyde and 2-methyl-1,3-dioxolane. The concentrations of acetaldehyde increased from 1.24-1.96 mg kg(-1) to 1.94-3.65, 3.52-7.23 and 5.45-15.37 mg kg(-1) after exposure to 5, 25 and 50 kGy doses, respectively. The concentrations of 2-methyl-1,3-dioxolane decreased from 2.49-5.26 mg kg(-1) to 2.07-3.13, 1.33-2.14 and 0.64-2.24 mg kg(-1) after exposure to 5, 25 and 50 kGy doses, respectively. The results of analysis of the copolymers for non-volatiles show that irradiation did not produce any new detectable non-volatile chemicals. A 5 kGy dose had no detectable effect on either copolymer. The 25 and 50 kGy doses had slightly different effects with respect to gamma- and e-beam irradiation on low MW oligomers. However, these increased doses did not significantly affect migration. The concentration of most low molecular weight oligomers migrating into 10% ethanol and 100% heptane wasor =2 ng g(-1) of each oligomer for both copolymers. The cyclic trimer migrating from the 3% CHDM copolymer was approximately 4 ng g(-1); it was 3 ng g(-1) for the 31% CHDM copolymer. The overall results suggest that irradiation significantly increased levels of acetaldehyde but had no effect on non-volatile compounds migrating into food simulants.

Migration of the diglycidyl ether of bisphenol A (DGEBA) to food from can enamels and can pull-top seals is reported. Derivatives of DGEBA are also determined in some foods. Levels of DGEBA in the foods surveyed in this study range from nondetected (

Migration of bisphenol A (BPA) from epoxy-coated can surfaces to infant formula concentrates is reported. Levels of BPA in the undiluted concentrates surveyed in this study range from 0.1 to 13 parts per billion (ppb) as determined by solid phase extraction/high-pressure liquid chromatography with fluorescence detection and confirmation by gas chromatography with mass selective detection. Fourier transform infrared spectroscopy with 30° specular reflectance/transmittance was used to screen formula cans for epoxy coatings. Keywords: Bisphenol A; epoxy; can coating; migration; infant formula

Bisphenol-A (BPA) is a principal reactant in the preparation of polycarbonate (PC) plastics and has been shown in in vitro cell proliferation studies to exhibit estrogen-like characteristics. Reusa...

A limited number of soft drinks, juices, beers, and waters from processed vegetables were analyzed for trihalomethanes (THMs), benzene, and toluene by a modified Environmental Protection Agency (EPA) Method 524.2. The THMs, which include chloroform, bromodichloromethane, dibromochloromethane, and bromoform, are reaction by-products of water disinfection by chlorination. EPA Method 524.2 is a purge-and-trap capillary gas chromatographic method based on mass spectrometric detection which identifies and simultaneously measures purgeable volatile organic compounds in drinking water. Chloroform was present at concentrations ranging from none detected to 94 ng/g in the 44 foods analyzed. Bromoform was not found in any of the products at a detection limit of 0.1 ng/g. Residue levels of the other THMs ranged from none detected to highs of 12 and 2 ng/g for bromodichloromethane and drbromochloromethane, respectively. Benzene residues were typically

Microwave heat susceptors that convert electromagnetic energy to heat attain high temperatures that make it possible to cook some foods to golden crispness in a microwave oven. Susceptors are typically packaged with foods intended for microwave use, e.g., waffles, pizzas, and french fries. The high temperatures >302°F used to cook some foods release trace levels of volatile chemicals from metalized polyester film, adhesive, and paper packaging materials; these volatile chemicals may be absorbed by the food. We simulated microwave susceptor cooking conditions and developed protocols by using headspace concentration capillary gas chromatography and mass spectrometry to identify volatile chemicals released from heated susceptors. We purchased a limited, cross-sectional sample of local retail microwave food products packaged with susceptors and used our protocol to analyze 10 different susceptor products. Although more than 140 unique chromatographic peaks were tabulated, only 44 volatile chemicals were identified, including 1,1,1-trichloroethane, benzene, and 2-(2-butoxyethoxy)ethanol, which were derived primarily from the paper and adhesive susceptor components. No one susceptor contained all the identified substances. The standard additions technique was the preferred method for quantitation. Trichloroethane and 2-(2-butoxyethoxy)ethanol were present in several products at 75-122 μg/in.2 of susceptor surface area. Benzene was found in 3 susceptors at ≤0.22 μg/in.2 levels. Examination indicates that adhesives used in more recent susceptor products were reformulated to remove even this trace level of benzene.

Recently, the combination of sodium or potassium benzoate with ascorbic acid was shown to produce low levels (ng/g) of benzene in fruit-flavored soft drinks. The presence of benzene also was reported in butter, eggs, meat, and certain fruits; levels of these findings ranged from 0.5 ng/g in butter to 500-1900 ng/g in eggs. Because benzoates are widely used as food preservatives, a limited survey of other foods containing added benzoate salts was conducted to investigate the potential for benzene formation. Selected foods that did not contain added benzoates but were previously reported to contain benzene were analyzed for comparison. More than 50 foods were analyzed by purge-andtrap or static headspace concentration and capillary gas chromatography. Benzene was quantitated by using the method of standard additions, and its identity was confirmed by mass selective detection. Results of this limited survey show that foods without added benzoates (including eggs) contained benzene at levels equal to or less than 2 ng/g. Slightly higher levels were present in some foods and beverages containing both ascorbic acid and sodium benzoate.

Furan is a suspected human carcinogen that is formed in some processed foods at low ng per g levels. Recent improvements in analytical methodology and scientific instrumentation have made it possible to accurately measure the amount of furan in a wide variety of foods. Results from analysis of more than 300 processed foods are presented. Furan was found at levels ranging from non-detectable (LOD, 0.2-0.9 ng g(-1)) to over 100 ng g(-1). Exposure estimates for several adult food types were calculated, with brewed coffee being the major source of furan in the adult diet (0.15 microg kg(-1) body weight day(-1)). Estimates of mean exposure to furan for different subpopulations were calculated. For consumers 2 years and older, the intake is estimated to be about 0.2 microg kg(-1) body weight day(-1).

Benzene, a carcinogen that can cause cancer in humans, may form at nanogram per gram levels in some beverages containing both benzoate salts and ascorbic or erythorbic acids. Through a series of reactions, a hydroxyl radical forms that can decarboxylate benzoate to form benzene. Elevated temperatures and light stimulate these reactions, while sugar and ethylenediaminetetraacetic acid (EDTA) can inhibit them. A headspace gas chromatography/mass spectrometry method for the determination of benzene in beverages was developed and validated. The method was used to conduct a survey of 199 soft drinks and other beverages. The vast majority of beverages sampled contained either no detectable benzene or levels below the U.S. Environmental Protection Agency’s drinking water limit of 5 ng/g. Beverages found to contain 5 ng/g benzene or more were reformulated by the manufacturers. The amount of benzene found in the reformulated beverages ranged from none detected to 1.1 ng/g.

A headspace gas chromatography/mass spectrometry method was developed and validated in-house for the determination of furan in foods. The method of standard additions with d4-furan as the internal standard was used to quantitate furan. The limit of detection and limit of quantitation (LOQ) values ranged from 0.2 and 0.6 nglg, respectively, in apple juice to 0.9 and 2.9 ng/g, respectively, in peanut butter. Recoveries were obtained at 0.5, 1, 2, and 3 times the LOQ. At 1, 2, and 3 times the LOQ, the recoveries ranged from 89.4 to 108%, and the relative standard deviations ranged from 3.3 to 17.3% for all the matrixes. For apple juice, chicken broth, and infant formula, the averaged coefficients of determination from the linear regression analyses were0.99 with each food fortified at 0.5, 1, 2, and 3 times the LOQ. The coefficients of determination were0.99 for green beans and 0.96 for peanut butter with the foods fortified at 1, 2, and 3 times the LOQ. Within-laboratory precision was determined by comparing the amounts of furan found in 18 samples by 2 analysts on different days with different instruments. For most of the foods, the difference between the amounts found by each analyst was18%. The method was used to conduct a survey of300 foods. The furan levels found ranged from none detected to 174 ng/g.

To evaluate the feasibility of recycling all PET bottles into food packaging, realistic estimates of the maximum concentration of contaminants that might be expected in the polymer are needed. To estimate the maximum concentration of a contaminant that might be in PET from the storage of non-food substances, sorption experiments into two types of PET were performed. These test materials were 0.8mm thick amorphous PET (a relative sink for contaminants) and commercial PET bottle wall. Using a commercial shampoo containing 1% lindane (C6H6Cl6), the test materials were stored in contact with the shampoo at 20 and 40 degrees C for 231 days. This commercial shampoo also represents an extreme case because it contains 7% acetone, a solvent which swells PET, further enhancing sorption of chemicals. Additional sorption experiments into PET were performed by preparing solutions of 10% toluene in Miglyol (a fractionated coconut oil), 10% benzophenone in Miglyol, 5% 2-butoxyethoxy ethanol (2-BE) in 50/50 water/ethanol, and 10% methyl stearate in heptane. Sorption data from the shampoo into PET illustrate Fickian behaviour. Specifically, the amount of sorption at room temperature is approximately40 times less than that at 40 degrees C. The amount of lindane sorbed into PET from the shampoo after 231 days was 0.1 and 3.7 mgdm(-2) at 20 and 40 degrees C respectively. These values correspond to 28 and 765 mg kg(-1) on a mass/mass basis. All sorptions are within the ranges measured and published by other authors using surrogate contamination testing schemes. Additionally, actual bottles from recycle bins were analysed for the amout of contamination. Results are discussed in terms of potential consumer exposure to non-food contaminants in food containers made of recycled PET and in relation to the surrogate testing methods recommended by the Food and Drug Administration (FDA) for determining the compatibility of a PET recycling process to produce containers suitable for food-contact use.

A gas chromatographic method is described for acrylonitrile monomer (AN), using a nitrogen/phosphorus detector. Procedures for the analysis of AN in 5 food simulants (water, 3% acetic acid, heptane, 50% ethanol, and 8% ethanol) as well as in the polymer matrix are included. The quantitation limit for direct injection of AN/food simulant solution is 0.04 ng AN/μl. AN-based polymers are dissolved in N,N-dimethylacetamide and injected directly. Residual AN in the polymer can be quantitated at the 0.5 ng/μl level. Results of migration studies are also presented.

A procedure was developed for determining acrylonitrile (AN) in 3% acetic acid, the solvent used to simulate carbonated beverages. Manual headspace sampling, a detector output amplifier/filter, and vapor phase enhancement using an ionic material were combined to give a detection limit in the low parts per trillion range. AN standards were analyzed using the method, and the results are presented.

Acrylonitrile (AN) in aqueous food-simulating solvents is concentrated by adding methanol and distilling the AN-methanol azeotrope. AN in heptane is partitioned into water and azeotropically distilled with methanol. This procedure concentrates approximately 30% of the An in 0.5 ml methanolic solution. The concentrate obtained is analyzed by gas-solid chromatography (GSC) and the presence of AN is confirmed by GSC-mass spectrometry, using multiple ion monitoring of ions at m/z 53, 52, 51, and 26. Levels as low as 0.01 ppm AN in the original food-simulating solvents can be confirmed. The migration of AN into 8% ethanol and 3% acetic acid contained in styrene-acrylonitrile bottles has been confirmed by using this method.

A screening procedure, using manual headspace sampling and gas-solid chromatography, is described for the determination of residual acrylonitrile (RAN) in acrylonitrile-based copolymers. The polymers are dissolved in dimethylsulfoxide; the resulting solutions are equilibrated in a closed container at 90°C, and headspace aliquots are injected into a gas chromatograph. A nitrogen-phosphorus selective detector and the method of standard additions are used for quantitation. RAN is measured down to 70 ppb (polymer basis) with a standard deviation of 7%. Polymers analyzed by this method had RAN levels from 0.07 to 23.9 ppm.

Gas-solid chromatographic (GSC) procedures are described for the analysis of Saran films for vinylidene chloride (VdC) and for determining the level of VdC migration from Saran film into 3 food-simulating solvents. The films are dissolved in tetrahydrofuran and analyzed for VdC by direct injection of the polymer solutions. VdC migration from Saran film to corn oil, heptane, and water is measured by headspace GSC. With electron capture detection and confirmation by GSC-mass spectrometry fragmentography, about 1 ppm VdC can be quantitated in the polymer and 5–10 ppb in the food simulants. Data for VdC migration from 2 commercial Saran films into the food simulants are presented to demonstrate the utility of the method.

The determination and confirmation of residual vinyl chloride (VC) in polyvinyl chloride (PVC) food packaging materials are described. PVC packaging materials are dissolved in dimethylacetamide (DMAC). VC is sparged from solution with helium gas and collected in sealed vials of ethanol. VC is detected and quantitated by using a headspace sampling technique and standard gas-solid chromatography (GSC) with flame ionization detection. GSC peak heights of about 5% full scale deflection are obtained for samples of PVC containing 1 ppb VC. Polymer samples taken from tubing, blood bags, food packaging films, bottles, and unprocessed resin were analyzed. Residual VC levels ranged from 0.3 to 913 ppb. VC was confirmed by GSC-mass spectrometry, using selected ion recording of m/z 62 and 64 in conjunction with full mass scans to identify components eluting near VC.

A headspace gas chromatographic procedure has been developed for the determination of 1,3-butadiene in rubber-modified plastics and in some foods. Polymer solutions or foods are equilibrated in sealed vials at 90°C, and headspace samples are injected into a gas chromatograph. 1,3-Butadiene residues are measured using a flame ionization detector and are quantitated by the method of standard additions or an external calibration curve. Refrigerator tubs, vegetable oil bottles, chewing gum, and foods in contact with this type of packaging were analyzed. Limits of quantitation varied with the matrix, ranging from 2 ng/g (ppb) in chewing gum to 20 ng/g in polymers. 1,3-Butadiene was found in one polymer at 53 ng/g with an 8% coefficient of variation. The procedure yields "apparent" trace levels of 1,3-butadiene, and confirmation by a complementary technique is required.